Phenyl-azo-phenyl dyestuffs

ABSTRACT

WHEREIN D monocyclic or bicyclic diazo residue; d is hydrogen, alkyl, or alkoxy; R is alkyl, R&#39;&#39; is alkyl or aryl; and R1 and R2 are hydrogen, alkyl, alkyl-carbonyloxy alkyl, hydrogen ethyl or cyanoethyl only one of R1 and R2 being hydrogen at one time. The dyestuffs are useful for dyeing polyester fibers.   Monoazo dyestuffs of the formula

United States Patent Inventor Ved Parkash Kubba Bombay, India Appl. No.705,027 Filed Feb. 13, 1968 Patented Dec. 7, 1971 Assignee Cilia LimitedBasel, Switzerland Priorities Feb. 21, 1967 Switzerland 2515/67;

Jan. 5, 1968, Switzerland, No. 120/68 PHENYL-AZO-PHENYL DYESTUFFS 6Claims, No Drawings US. Cl 260/205, 260/158, 260/206, 260/207,260/207.1,

8/5, 8/41 R, 8/4] A, 8/41 B, 8/41 C, 8/41 D, 8/50 Int. Cl C07c 107/06,C09b 29/06 Field of Search 260/205,

Primary Examiner--Charles B. Parker Assistant Examiner-Charles F. WarrenA!t0rneysl-larry Goldsmith, Joseph G. Kolodny, Bryant W.

Brennan and Edward J. Sites IBA Mq p z estuff ss f e rmyle 0.-

N(SO2R) (SOzR') wherein D monocyclic or bicyclic diazo residue; d ishydrogen, alkyl, or alkoxy; R is alkyl, R is alkyl or aryl; and R and Rare hydrogen, alkyl, alkyl-carbonyloxy alkyl, hydrogen ethyl orcyanoethyl only one of R and R being hydrogen at one time. The dyestuffsare useful for dyeing polyester fibers.

PHENYL-AZO-PHENYL DYESTUFFS The present invention relates to new andvaluable dyestuffs which contain at least one disulfonylamino group ofthe formula N(SO R) particularly azo dyestuffs in which at least one azoor diazo component contains at least one disulfonylamino group of theformula N(SO,,R) bound to an aromatic nucleus externally, but preferablydirectly, in which formula R represents the radical of an organicmonosulfonic acid which has been freed from the sulfone group,preferably an alkyl radical.

The new dyestuffs may be obtained either by 0. using at least one diazoor azo component containing at least one disulfonylamino residue of theformula -N(SO R), during manufacture, which is effected by coupling, or

b. by sulfonylating the already formed azo dyestuff, which contains atleast one unsubstituted amino group or sulfonylamino group of theformula -NH(SO R) preferably bound directly to the aromatic nucleus, atthe free hydrogen atoms of the said amino group to form the disulfonylderivative.

The invention relates, in particular, to water-insoluble monoazodyestuffs of the formula D-N=N-A, in which D represents a benzeneresidue or a heterocyclic residue and A represents a benzene residuecontaining a substituted amino group which is preferably inpara-position to the azo group, and in which at least one of the tworesidues D and A, but preferably A, contains as substituent at least onegroup of the formula--N(SO,,R) in which R has the meaning given above.

Dyestuffs which are of special interest are those of the formula inwhich is bound preferably in a position vicinal to the amino group anddis bound preferably in a position vicinal to the azo group, and inwhich c and 11 represent hydrogen atoms, halogen atoms, low alkyl andalkoxy groups, for example, methyl, ethyl, methoxy and ethoxy groups,arylthio and aryloxy residues, for example, phenylmercapto and phenoxyresidues or residues of the formulas N(SO,R)= or NH- 50 R, in which Rrepresents an organic residue, preferably an alkyl residue having one to18 carbon atoms, R, represents a hydrogen atom, the group of the formulaSO R or preferably an alkyl group which may be substituted especiallythe group -alkyleneN(SO R),, and R, represents an alkyl group which maybe substituted or an acyl group, especially the group of the formula SOR or -alkyleneN(SO R) When R, and R do not contain SO R groups and Dcontains no N(SO R)', groups, c is an N(SO,R) group.

The groups R, and R may be low alkyl groups containing one to four, butpreferably two to four, carbon atoms, for example, methyl, ethyl,n-propyl or n-butyl groups which may be substituted in the usual manner,for example, halogenated alkyl groups, for example, B-chloroethyl, B, B,B-trifluoroethyl or B, 'y-dichloropropyl groups, B-cyanoethyl groups,alkoxyalkyl groups, for example, fl-ethoxyethyl or 8-methoxybutylgroups, hydroxyalkyl groups, for example, B-hydroxyethyl or B,'y-dihydroxypropyl groups, nitroalkyl groups, for example, B-nitroethylgroups, carbalkoxy groups, for example, B-carbo- (methoxy-, ethoxyorpropoxy)-ethyl groups (in which the terminal alkyl group may carrycyano, carbalkoxy, acyloxy or amino groups in w-position), B- or'y-carbo-(methoxyor ethoxy)-propyl groups, acylaminoalkyl groups, forexample, B-(acetylor formyl)-aminoethyl groups, acyloxyalkyl groups, forexample, fl-acetyloxyethyl or B, 'y-diacetoxypropyl groups, B-(alkyloraryl)-sulfonylalkyl groups, for example, B- methanesulfonyl-ethyl,B-ethanesulfonylethyl or B-(parachlorobenzenesulfonyl)-ethyl groups,alkylor arylcarbamoyloxyalkyl groups, for example, B-methylcarbamyloxga-cm SOaOHa CHa-CHr-N S02CH3 OCH;

CHr-CH;

-N SOQCHQCHs CHz-CHzN and especially the amines of the formulas Thepreferred diazo component D-NH an aminobenzene, especially one of theformula in which a is in 3-position, but preferably in Z-position and bis in 6-position, but preferably in 5-position and a represents ahydrogen or a halogen atom or an alkyl group, an alkoxy group, a phenoxygroup, a nitro group, a cyano group, a car balkoxy group, an N-monoorN,N-dialkylsulfonamide group or an alkysulfone group, b represents ahydrogen or a halogen atom or an alkyl group, a cyano group or atrifluoromethyl group and c represents a hydrogen or a halogen atom oran alkyl group, an Nvmonoor N,N-diallcylsulfonamide group, a carbalkoxygroup or an alkylsulfonyl group and especially a nitro group, or a, band/or c represent the above-mentioned -N(SO R) group.

The following may be mentioned as examples: aminobenzene,l-amino-4-chlorobenzene, l-amino-4- bromobenzene,l-amino-4-methylbenzene, l-amino-4- nitrobenzene,l-amino-4-cyanobenzene, l -amino-2,5-

dicyanobenzene, l-amino-4-methylsulfonylbenzene, l-amin'o-4-carbalkoxybenzene, l-amino-2,4-dichlorobenzene,lamino-2,4-dibromobenzene, l -amino-2-methyl-4- chlorobenzene,l-amino-2-trifluoromethyl-4-chlorobenzene,l-amino-2-cyano-4-chlorobenzene, l-amino-2-carbomethoxy-4-chlorobenzene,l-amino-2-carbomethoxy-4-nitrobenzene, l-amino-2-chloro-4-cyanobenzene,l-amino-2-chloro-4- nitrobenzene, l-amino-2-chloro-4-carbethoxybenzene,1- amino-2-phenoxy-4-nitrobenzene, l-amino-2-chloro-4-methylsulfonylbenzene and l-amino-2-methylsulfonyl-4- chlorobenzene.

l-amino-2-methylsulfonyl-4-nitrobenzene, l-amino-2,4- dinitrobenzene,l-amino-2,4-dicyanobenzene, l-amino-2- cyano-4-methylsulfonylbenzene,1-amino-2,6-dichloro-4- cyanobenzene,l-amino-2,6-dichloro-4-nitrobenzene, lamino-2,4-dicyano-6-chlorobenzene,l-amino-2,4-dinitro-6- chlorobenzene and especially l-amino-2-cyano-4-nitrobenzene; furthermore, l-aminobenzene-2- or -4-sulfonic acid amides,for example, N-methyl or N,N-dimethyl or diethyl amide.

The following amines may be mentioned from the heterocyclic diazocomponent series: 2-aminothiazole, 2-amino-5-cyanothiazole, 2-amino-4-methyl-S-nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4-(4'-chloro)-phenylthiazole, 2-amino-4-(4-nitro)-phenylthiazole, 2-amino-6- chlorobenzthiazole,2-amino-6-methylsulfonylbenzthiazole, 2- amino-fi-cyanobenzthiazole,2-amino-6-nitrobenzthiazole, 2- aminol ,3,4-thiadiazole,-amino-3-phenyll ,2,4-thiadiazole, 2-amino-l,3,5-thiadiazole andespecially 2-amino-5- nitrothiazole.

MANUFACTURING PROCESS (a) Diazotization of the above-mentioned diazocomponents may be carried out by known methods, for example, with theaid of a mineral acid and sodium nitrate or, for example, with asolution of nitrosyl sulfuric acid in concentrated sulfuric acid.

Coupling may likewise be carried out in known manner, for example, in aneutral to acid medium, if necessary, in the presence of sodium acetateor a similar buffer which influences the rate of coupling, or acatalyst, for example, pyridine, or a salt thereof.

After coupling, the dyestuff formed may easily be isolated from thecoupling mixture, for example, by filtration, because it is virtuallyinsoluble in water.

The new components required for the coupling process are prepared in thefollowing manner:

N-sulfonylation of sulfonylamino groups or preferably unsubstitutedamino groups, which are preferably bound directly to an aromaticnucleus, is carried out by known methods, especially by reaction withthe corresponding sulfonyl halides RSO,-hal, in which R has the meaninggiven above, but is preferably an alkyl group, especially alow-molecular alkyl group having up to four carbon atoms.N-sulfonylation may be carried out in an inert organic solvent or in atertiary amine, for example, pyridine, or especially in an aqueousmedium when the azo or diazo component is used as starting material, inwhich case it is expedient to add an acid acceptor, for example, atertiary amine.

ln addition to the aromatic monosulfonic acid halides, for example,paratoluenesulfonic acid chloride and parabromobenzenesulfonic acidchloride, mention may also be made, in particular, of the sulfonic acidchlorides with low alkyl groups, especially those having a methyl orethyl group.

MANUFACTURING PROCESS (b) When an azo dyestuff which has already beenformed is used as starting material it must contain at least onemonosulfonylamino group or preferably an unsubstituted amino group. Bystarting from monoalkylsulfonyl-amino groups in the starting dyestuffs,such as are described, for example in French Pat. No. 1,350,486, inBritish Pat. No. 865,409 or in German Pat. No. 1,078,992, it is possibleby reaction with an aromatic monosulfonic acid halide to obtaindyestuffs whose amino group carries both an aryl-sulfonyl group and analkylsulfonylamino group. Since preference is given to water-insolubleazo dyestuffs, N-sulfonylation is preferably carried out in an organicsolvent in the case of azo dyestuffs.

When the amount of sulfonic acid halide used is less than that requiredto bring about twofold substitution of all unsubstituted amino groups, amixture of the monosulfonylaminoazo dyestuff and the disulfonylamino-azodyestuff is obtained, which, however, may also be produced by subsequentmixing.

The new dyestuffs, mixtures thereof, and mixtures of the new dyestuffswith other azo dyestuffs are eminently suitable for dyeing and printingsynthetic fibers, especially when they have been converted into a stateof fine division, for example, by grinding, pasting, reprecipitation,and so forth. This invention therefore also relates to a process fordyeing or printing synthetic fibers, for example, acrylic fibers oracrylonitrile fibers, or fibers of polyacrylonitrile or of mixedpolymers of acrylonitrile and other vinyl compounds, such as acrylicesters, acrylic amides, vinylpyridine, vinyl chloride or vinylidenechloride, mixed polymers of dicyanoethylene and vinyl acetate, or ofacrylonitrile block copolymers, fibers of polyurethanes, cellulose triorZk-acetate, polyamides, such as nylon 6, nylon 6,6 or nylon 10, andespecially fibers of aromatic polyesters, such as fibers of terephthalicacid and ethylene glycol or 1,4-dimethylolcyclohexane, and mixedpolymers of terephthalic acid and isophthalic acid and ethylene glycol,in which process use is made of azo dyestuffs which contain at least onedisulfonylamino group of the formula N(SO R) particularly azo dyestuffsin which at least one azo or diazo component contains at least onedisulfonylamino group of the formula -N(SO R) bound to an aromaticnucleus externally, but preferably directly, in which formula Rrepresents the radical of an organic monosulfonic acid which has beenfreed from the sulfone group, preferably an alkyl radical.

As a rule, the new dyestuffs have a greater affinity to polyester fiberswhich are the preferred substrate than to the correspondingmonosulfonylamino derivatives. They produce pure, strong dyeingspossessing an excellent fastness to light and to sublimation on aromaticpolyester fibers when applied by the usual dyeing processes, forexample, when applied in the form of a fine dispersion in a dyebath,which advantageously contains a dispersing agent, at a temperature closeto 100 C., if necessary, in the presence of a swelling agent, or at atemperature above 100' C. under superatmosphere pressure. The fastnessto light and sublimation as a rule surpasses that of themonosulfonylamino derivatives, the new dyestuffs also have the advantagethat they produce only very slight staining on any wool, acetate, nylon,or other fibers that may be present in the dyebath, and are thus verysuitable for dyeing polyester/wool, and especially polyester/triacetateand polyester/nylon mixtures; reservation of acetate and nylon is betterthan that of comparable dyestuffs.

The dyestuffs of the invention are also suitable for application by theso-called Thermosol process in which the material to be dyed isimpregnated at a temperature not exceeding 60 C. with an aqueousdispersion of the dyestuff which advantageously contains 1 to 50 percentof urea and a thickening agent, especially sodium alginate, and thensqueezed in the usual manner, advantageously in a manner such that theimpregnated material retains 50 to 100 percent of its dry weight ofdyeliquor. To fix the dyestuff, the impregnated fabric is dried, forexample, in a current of warm air, and then heated to a temperatureabove 100' C., for example, to a temperature between 1 and 210 C.

The Thermosol process is specially suitable for dyeing union fabricsmade from polyester fibers and cellulosic fibers, especially cotton andalso, in particular, unions made from polyester and nylon or acetatefibers. Special mention should be made of their greater afiinity andsuperior fastness to light compared with similar dyestuffs.

The dyestuffs of this invention are also suitable for dyeing textilematerials, especially union fabric from suitable cellulose-based fibersand fully synthetic fibers, which are finished by the so-calledPermanent-Press or Durable-Press process. In these processes, a curableprecondensate is applied to the dyed fabric together with an at leastpotentially acid or latently acid catalyst, and the final shape is giventhe wearing apparel by condensing the artificial resin finish. Such aprocess is described, for example in US. Pat. No. 2,974,432.

Some of the new products are also valuable pigments which can be usedfor a very wide variety of purposes. For example, they can be used in astate of fine division for the spin-coloration of filament andstaple-fiber viscose, cellulose ethers and esters, polyamides,polyurethanes and polyesters, and in the production of colored lacquersor lake-formers, solutions and products made from acetylcellulose,nitrocellulose and natural resins and synthetic resins, for example,polymerization resins or condensation resins, for example, aminoplasts,alkyd resins, phenoplasts and polyolefins, for example, polystyrene,polyvinyl chloride, polyethylene, polypropylene and polyacrylonitrile,rubber, casein, silicones and silicone resins.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

I. Manufacture of the Starting Components Example 1 28.63 Parts ofmethanesulfonyl chloride and 25.3 parts of triethylamine as acidacceptor are added to a solution of 13.6 parts ofmeta-amino-N,N-dimethylaniline in 600 parts of anhydrous benzene. Thesolution is boiled under reflux for 12 to hours. The solvent isdistilled under reduced pressure, and the residue is dissolved in 25parts by volume of ether to isolate unreacted starting material. Theether solution is decanted and the brown residue is recrystallized threetimes from dilute alcohol. 15.1 parts ofmeta-bis-(N-methanesulfonyl)amino-N,Ndimethylaniline are obtained in theform of white platelets melting at 154 to 155 C.

Example 2 A solution of 10.0 parts of sodium hydroxide in 30 parts ofwater and 28.63 parts of methanesulfonyl chloride are addedsimultaneously in the course of 45 minutes to a suspension of 13.6 partsof meta-amino-N,N-dimethylaniline in 200 parts of water, whichsuspension is kept at a temperature of 10 C. The mixture is stirred for2 to 3 hours. The water is decanted and the viscous residue is treatedwith 30 parts of ether. The solid brown residue obtained isrecrystallized twice from dilute alcohol. 12.7 Parts ofmeta-bis(N-methanesulfonyl)amino- N,N-dimethylaniline are obtained inthe form of white platelets melting at 154 to 155 C.

Example 3 Methanesulfonyl chloride is reacted with a solution of 16.4parts of meta-amino-N,N-diethylaniline in the manner described inexample 1. 16.5 Parts of meta-bis(N'- methanesulfonyl)-amino-N, N-diethylaniline are obtained in the form of white platelets melting at151 to 152 C.

Example 4 Methanesulfonyl chloride is reacted with 16.4 parts ofmeta-amino-N,N-diethylaniline in the manner described in example 2. 11.0Parts of meta-bis(N-methanesulfonyl)amino- N,N-diethylaniline areobtained in the form of white platelets melting at 151 to 152 C.

Example 5 The procedure is an in example 1, except that themethanesulfonyl chloride is replaced by an equivalent quantity ofethanesulfonyl chloride and that toluene is used as solvent. A brownsolid residue is obtained which when recrystallized yields thecrystalline meta-bis(N'diethylsulfonyl)amino- N,N-dimethylanilinemelting at 111 -l 12 C.

Example6 From an equivalent quantity of meta-amino-N,N-

diethylaniline there is obtained the procedure of example 5 puremeta-bis(N'-diethylsulfonyl)amine-N,N-diethylaniline melting at 106 107C.

Example 7 A solution of 0.1 mol of N-(N'-methanesulfonyl-2-aminoethyl)-N-ethyl-meta-toluidine (prepared according to Journal of theAmerican Chemical Society, Vol. 73, page 3100 (1951) in 400 parts ofxylene (dried over sodium metal) is treated with 0.15 mol of lithiummetal and refluxed for -100 hours. When the batch has cooled a slightexcess over 0.15 mol of methane sulfonyl chloride is added and themixture refluxed for 8 hours. After cooling, the batch is filtered andthe precipitated lithium chloride washed with dry benzene. The solventsare combined and evaporated and the residue distilled under reducedpressure. After the first fraction, which consists of unchanged startingmaterial, there is obtainedN-B-N',N-dimethanesulfonylamino)ethyl-N-ethylmeta-toluidine of theformula A y Calculated found 11. Manufacture of the Dyestuffs Example I4.31 Parts of 2-chloro-4-nitraniline are diazotized at room temperaturewith nitrosylsulfuric acid prepared from 40 parts by volume ofconcentrated sulfuric acid and 2 parts of sodium nitrite. The excess ofnitrous acid is destroyed with urea and the reaction mixture isfiltered. The solution obtained is coupled at 5 to 10 C. with 7.3 partsof meta-bis(N'-methanesulfonyl)amino-N,N-dimethylaniline in a. mixtureof 40 pans of alcohol and 250 parts of water, the batch being stirredfor 5 hours or longer until coupling is finished. The pH value isadjusted to 4 to 5 at a temperature of below 10 C. with a 4N sodiumacetate solution and the dyestuff is isolated by filtration and washedwith a large amount of water. Subsequently, the dyestuff is suspended in500 parts of water, the suspension is rendered alkaline with a smallamount of sodium carbonate solution and then acidified with acetic acid.In some cases it may be necessary, in order to remove starting materialand impurities, to treat the dyestuff with acetone and to precipitatethe dissolved dyestuff with water. The dyestuff obtained, whichcorresponds to the formula l 3 Cl N(SO2CH )2 dyes polyester fibersred-violet tints possessing excellent pro perties of fastness whenapplied in the form of an aqueous dispersion.

DYEING PRESCRIPTION 1 Part of the dyestuff obtained in the mannerdescribed above is ground wet with 2 parts of a 50 percent aqueoussolution of the sodium salt of dinaphthylmethanedisulfonic acid and thebatch is then dried.

The dyestufi' preparation so obtained is mixed with 40 parts of apercent aqueous solution of the sodium salt of N- diazonium salt iscoupled in the manner described in example l. The dyestuff obtained,which corresponds to the formulabenzyl-n-heptadecylbenzimidazoledisulfonic acid and then 4 CH3 parts ofan acetic acid solution of percent strength are added. A dyebath of4,000 parts is prepared therefrom by 5 3 dilution with water. 0N N sOQCHOZ l00 Parts of cleansed polyester fiber material are entered dyespolyester fibers violet tints possessing excellent properinto thisdyebath at C., the temperature is raised to 120 C ties of fastness whenapplied in the form of an aqueous disperto l30 C. within 30 minutes anddyeing is carried out for one l0 sion. hour at that temperature in aclosed vessel. The material is The following table lists components offurther dyestuffs subsequently well rinsed. A strong, pure, red-violetdyeing which are obtained when the diazo component shown in possessingan excellent fastness to light and to sublimation is column 3. Column 4indicates the tint obtained on polyester obtained. fibers.

Column Example No.1

IV CH Reddish yellow.

OzN- NII CH; N s 0 011 Same as above Claret.

OzN- -NHg VI ,....do .A Red.

OzN- -NH2 VII do Do.

I OCH;

VIIL. d0 Reddish O2N NH: violet l S 020B;

IX do.. Yellowish CHaOzS- -NH2 red.

I Cl

X 1'31 do Violet.

O2NC NH2 XI Cl do Do.

Example ll Example Xll 5.17 Parts of 2,6-dichloro-4-nitraniline arediazotized in the manner described in example 1, and the filteredsolution of the diazonium salt is coupled and worked up in the mannerdescribed in that example.

The dyestuff obtained, which corresponds to the formula dyes polyesterfibers blue-red tints possessing excellent properties of fastness whenapplied in the form of an aqueous dispersion.

Example Ill 4.] Parts of 2-cyano-4-nitraniline are diazotized in theCzHs 0 dyes polyester fibers blue-violet tints when applied in the formmanner described in example l, but with an addition of 10 parts byvolume of acetic acid. The filtered solution of the of an aqueoussuspension.

The following table lists components of further dyestuffs which areobtained when the diazo components shown in column 2 are diazotized andcoupled with the coupling components shown in column 3. The tintsobtained with the dyestuffs on polyester fibers are indicated in column4.

19 lll Column I Example No.:

XIII CQHS Red.

O2N- NH2 C2116 N(S 02011 XIV Samcasabove Blue red.

zN- N112 XV ..d0 Rod-violet.

O2N NH:

XVI... .tlo Red.

OzN-- -NHg XVII do ltcd.

()2N NII2 l ()CI-la XVIII do...... Violet.

()QN "Nllj XIX ...do Yellow-red.

ClI30flS -NH2 XX.. Cl ....do Blue-red.

XXI. Ilir .undo Violet.

XXII... IOI d0. D0.

oils-Gou d ExampleXXIV 01 2.16 parts of 2-chloro-4-nitro-aniline arediazotized at room temperature with nitrosylsulfuric acid prepared from20 parts by volume of concentrated sulfuric acid and 1 part of sodiumnitrite. The excess nitrous acid is destroyed with urea, and thereaction mixture is filtered. The resulting solution is coupled at 5l0C. with 4.17 parts ofN-B-[(N',N-dimethanesulfonyI)-amino]-ethyl-N-ethyl-metatoluidine in amixture of parts of alcohol and 120 parts of water, then stirred for atleast 7 hours until coupling is complete, and the pH then adjusted to4-5 by the addition of 4N-sodium acetate solution at a temperature below10 C. The dyestuff which precipitates is filtered off, washed with muchwater, dissolved in acetone, and precipitated with water. A dyestuff ofthe formula CH3 .,,..VH is obtained which dyes polyester fibers bluishred tints having excellent fastness propertiesv Example XXV Theprocedure is that of example XXIV except for the use as diazo componentof 2.6 parts of 2,6-dichloro-4-nitroaniline. The dyestuff of the formula55 Cl CH3 Example XXVI 2.05 parts of 2-cyano-4-nitro-aniline arediazotized as described in example XXIV, but with the addition of 5parts by volume of acetic acid. Coupling and working up gives thedyestuffs of the formula ON CH:

CzHs

which dyes polyester fibers bordeaux-red shades having excellentfastness properties.

Example XXVII When the procedure of example XXIV is followed and N-B-[(N',N-dimethanesulfonyl)amino-ethyl-N-ethylmetatoluidine] replaced bythe N',N'-diethanesulfonylamino derivative there is obtained on workingup the dyestuff of the formula alcohol to give white needles ofmeta-(N'-benzene-su|fonyl)- amino-N,N-dimethylaniline G1 I CHa CH3 CHaCH3 W C? 9293??! which dyes polyester fibers bluish-red shades havingexcellent NHSO2 fastness properties. 1

The table below lists further dyestuffs that are obtained by To asolution f f l -N diazotizins the dim) components of column 2 andcoupling dimethylaniline 15.4 parts) in dry benzene 400 parts) was theproduct with the coupling components of column 3. added methane sulfonylchloride (13.4 parts) and an acid Column 4 shows the shades of thedyeings on polyester fibers binding agent, triethylamine (20.0 parts).The solution was obtained with the resulting dyestuffs. boiled at refluxfor hours. it was filtered and the solvent Column Example No.2 CH

XXVIII OzN NH2 -N/ Yellowish-red.

I CH3 N(SO2C2H5)2 Cl XXIX OzN-NH2 Same as above Do.

/C2H5 XXX OzN NH2 N\ Red.

I CH5 N(SO2C2H5)2 XXXI 02N -NH9 Same as above Bluish-red.

I Cl

Cl XXXII.- OzN-O-NH; 10 Yellowish-red.

XXXIIL". Oz--NH do Violet-red.

l l'oz CONTINUOUS DYEING OF POLYESTER FABRICS was removed under reducedpressure. The brown solid was I I I crystallized from alcohol (95percent) to give white needles of 20 Parts of t f -""'9 'Nmeta-(N'-benzene-sulfonyl-N-methane-sulfonyl)-aminodiethylsulfonyl)-am|no-N,N-d1methylamhneare ground with N'NdbmehYlanilinemp 0 07 140 parts of water containing40 parts of sodium dinaphthylmethanedisulfonate. 3

A padding liquor is prepared from 200 parts of the above C dyestuffpreparation, 100 parts of carboxymethyl cellulose (4 percent aqueoussolution) and 700 parts of water, by stirring the preparation into thepreviously prepared thickening, using NHS 0 a high-speed stirrer, andthen adjusting the pH to 6 by means 2 of 80 percent acetic acid. Apolyester fabric is padded in the S OZCH resulting liquor at 30 C. andsqueezed so as to retain 60 percent of its weight of liquor, then driedat 70-80 C. The fabric pans g amline are diazouzed at room a temperaturewith mtrosylsulfunc acid prepared from 20 parts lS then heated on astenter at 210 C. for 60 seconds, washed h t d d H d t Ab wn red d einis b by volume of concentrated sulfuric acid and one part of sod:- s zggf g z gs y g o um nitrite. The excess of nitrous acid is destroyed withurea g p p and the reaction mixture is filtered. The solution obtainedis coupled at 5 to 10 C. with 3.54 parts of meta-(N-benzene- Examplexxxlv sulfonyl-N'-methane-sulfonyl)-amino-N,N- dimethylaniline in To asolution of m-amino-N,N-dimethylaniline (13.6 parts) in dry benzene (400parts) was added benzene sulfonyl chloride (l9.5 parts) and an acidbinding agent, triethylamine (30.0 parts). The solution was boiled atreflux for 15 hours. It

was filtered and the solvent was removed under reduced pressure. Thebrown solid was crystallized three times from dilute acetic acid (200parts). The batch being stirred for 5 hours or longer until coupling isfinished. The pH value is adjusted to 4 at a temperature below 10 C.,with 4N sodium acetate solution and the dyestuff is isolated byfiltration and washed with water. In some cases, it may be necessary, inorder to remove starting material and impurities, to treat the dyestuffwith acetone and to precipitate the dissolved dyestuff with water. Thedyestuff obtained, which corresponds to the formula dyes polyesterfibers bluish red, possessing excellent properties of fastness whenapplied in the form of an aqueous dispersion.

Example XXXV 1.63 Parts of 2-cyano-4-nitroaniline are diazotized in themanner described in example XXXIV but with an addition of 5 parts byvolume of acetic acid. The filtered solution of the diazonium salt iscoupled with 3.54 parts of meta-(N'-benzene-sulfonyl-N'-methane-sulfonyl)-amino-N,N- dimethylaniline in themanner described in example XXXIV. The dyestuffs obtained, whichcorrespond to the formula dyes polyester fibers violet (hightemperature) and reddish violet (pad-dry heat), possessing excellentproperties of fastness when applied in the form of an aqueousdispersion.

Example XXXVI 2.04 Parts of 2:6-dichloro-4-nitroaniline are diazotizedin the manner described in example XXXlV. The filtered solution of thediazonium salt is coupled with 3.54 parts of meta-(N-benzenesulfonyl-N'-methane-sulfonyl)-amino-N,N- dimethylaniline inthe manner described in example XXXlV. The dyestuff obtained, whichcorresponds to the formula dyes polyester fibers reddish brownpossessing excellent properties of fastness when applied in the form ofan aqueous dispersion.

Example XXXVll To a solution of meta-(N'p-toluene sulfony1)-amino-N,N-dimethylaniline (18.1 parts) in dry benzene (400 parts) was addedmethane sulfonyl chloride (15.0 parts) and an acid binding agent,triethyl amine (23.0 parts). The solution was boiled at reflux for 20hours and worked up in the manner described above. It crystallized fromalcohol percent) to givemeta-(N-p-toluene-sulfonyl-N'-methane'sulfonyl)-N,N- dimethylaniline,m.p. 137-l 38 C.

1.73 Parts of 2-chloro-4-nitroanilihe are diazotized in the mannerdescribed in example XXXlV. The filtered solution of the diazonium saltis coupled with 3.68 parts ofmeta-(N'-ptoluene-sulfonyl-N'-methane-sulfonyl.)-N,N-dimethylaniline inacetic acid (200 parts) in the manner described in example XXXlV. Thedyestuff obtained which corresponds to the formula ClIa dyes polyesterfibers bluish red.

Example XXXVI" 1.63 Parts of 2-cyano-4-nitroaniline are diazotized inthe manner described in example XXXlV but with an addition of 5 parts byvolume of acetic acid. The filtered solution is coupled with 3.68 partsof meta-(N'-p-toluene-sulfonyl-N'-methanesulfonyl)-amino-N,N-dimethylaniline in acetic acid (200 parts),in the manner described in example XXXIV. The dyestuff obtained, whichcorresponds to the formula dyes polyester fiber reddish violet.

Example XXXIX 2.04 Parts of 2:6-dichloro-4-nitroaniline are diazotizedin the manner described in example XXXIV. The filtered solution of thediazonium salt is coupled with 3.68 parts of meta-(N-p-toluene-sulfonyl-N-methanesulfonyl)-amino-N,N- dimethylaniline inacetic acid (200 parts) in the manner described in example XXXIV. Thedlyestuff obtained, which corresponds to the formula I CH3 l CH: 01 I02-C om .9. 93

dyes polyester fiber reddish brown.

Example XXXX To a solution of m-amino-N,N-diethylaniline 16.4 parts) indry benzene (400 parts) was added benzene sulfonyl chloride (19.5 parts)and an acid binding agent, triethyl amine (28.0 parts). The solution wasboiled at reflux for 20 hours. The solvent was removed under reducedpressure and the solid was crystallized from dilute alcohol, to givenmeta-(N'-benzenesulfonyl)-amino-N,N-diethylaniline.

CzHs To a solution of meta-(N-benzenesulfonyl)-amino-N,N- diethylaniline(16.0 parts) in dry benzene (400 parts) was added methanesulfonylchloride (23.0 parts) and an acid binding agent, triethyl amine (30parts). The solution was boiled at reflux for 24 hours and worked up inthe manner described above. it crystallized from alcohol (95 percent) togive meta-( N -benzene-sulfonyl-N '-methane-sulfonyl )-amino-N,N-diethyl-aniline, m.p. l07-l08C.

[.73 Parts of 2chloro-4-nitroaniline are diazotized in the mannerdescribed in example XXXIV. The filtered solution is coupled with 3.82parts of meta-(N-benzene-sulfonyl-N'-methane-sulfonyl)-amino-N,N-diethylanaline in acetic acid (200 parts) inthe manner described in example XXXIV. The dyestuff obtained whichcorresponds to the formula dyes polyester his. bluish pink (hightemperature) and bluish red (pad-dry heat).

Example XXXXl 1.63 Parts of 2-cyano-4-nitroaniline are diazotized in themanner described in example XXXIV but with an addition of 5 parts byvolume of acetic acid. The filtered solution is coupled with 3.82 partsof meta-(N-benzene-sulfonyl-N'-methane-sulfonyl)-amino-N,N-diethylaniline in acetic acid 200 parts) inthe manner described in example XXXIV. The dyestuff obtained whichcorresponds to the formula CzH5 ON S OzOH;

dyes polyester fiber Violet.

Example XXXXll 2.04 Parts of 2:6-dichloro-4-nitroaniline are diazotizedin the manner described in example XXXIV. The filtered solution of thediazonium salt is coupled with 3.82 parts of meta-(N'-benzene-sulfonyl-N'-methane-sulfonyl)-amine-N,N- diethylaniline inacetic acid (200 parts) in the manner described in example XXXIV. Thedyestuff obtained which corresponds to the formula CzHa CzHs C1 li -S02- n S OQCH;

dyes polyester fiber reddish brown.

Example XXXXllI To a solution of m-amino-N,N-diethylaniline (16.4 parts)in dry benzene (400 parts) was added p-toluene sulfonyl chloride (20.95parts) and an acid binding agent, triethyl amine (28.0 parts). Thesolution was boiled at reflux for 22 hours. It was filtered. The solventwas removed under reduced pressure and the brown solid was crystallizedfrom dilute alcohol to give meta-(N-p-toluene-sulfonyl)amino-N,N-diethylaniline.

CzHs Q CzHs 1.73 Parts of 2-chloro-4-nitroaniline are diazotized in themanner described in example XXXIV. The filtered solution is coupled with3.96 parts of meta-(N-p-toluene-sulfonyl-N'-methane-sulfonyl)-amino-N,N-diethylaniline in acetic acid (200 parts) inthe manner described in example XXXIV. The dyestuff obtained, whichcorresponds to the formula CzHs ( 31 I \C2H5 dyes polyester fiber bluishpink (high temperature) and bluish red (pad-dry heat).

Example XXXXIV L63 Parts of 2-cyano-4-nitro-aniline are diazotized inthe manner described in example XXXlV but with an addition of 5 parts byvolume of acetic acid. The filtered solution is coupled with 3.96 partsof meta-(N'-p-toluene-sulfonyl-N'-methane-sulfonyl)-amino-N,N-diethylaniline in acetic acid (200 parts) inthe manner described in example XXXIV. The dyestuff obtained whichcorresponds to the formula M 7m V V SOzCHa dyes polyester fiber violet.

Example XXXXV 2.04 Parts of 2:6-dichloro-4-nitroaniline are diazotizedin the manner described in example XXXIV. The filtered solu' tion of thediazonium salt is coupled with 3.95 parts of meta-(N'-p-toluene-sulfonyl-N'in acetic acid (200 parts) in the mannerdescribed in example XXXlV. The dyestufi obtained, which corresponds tothe formula S O2CI Is dyes polyester fiber reddish brown Example XXXXVIN,N-di-( Z-cyanoethyl)-m-nitroaniline was reduced with tin andhydrochloric acid to give the correspond amine; which crystallized fromwater m.p. 9697 C.

CHzCHzCN To a solution of -m-amino-N,N-di-(2-cyan0ethyl)-aniline (10.7parts) in dry benzene (500 parts) was added methanesulfonyl chloride(17.25 parts) and an acid binding agent, triethylamine (20.2 parts).

The solution was boiled at reflux for 24 hours. The solvent was removedunder reduced pressure. The brown solid was washed several times withwater to remove triethylamine hydrochloride. The solid had m.p. 206 C.

CHzCHzCN 2.16 Parts of 2-chloro-4-nitroaniline are diazotized at roomtemperature in the manner described in example XXXlV. The filteredsolution of the diazonium salt is coupled with 4.63 parts ofmeta-bis-(N'-methane-sulfonyl)-amino-N,N-di(2- cyanoethyl)-aniline inacetic acid (150 parts) in the manner described in example XXXIV. Thedyestuff obtained which corresponds to the formula CH2 C H10 N N o.-N=N- N\ om om N Cl N S 02 C 113,)2

dyes polyester fiber scarlet (high temperature) and yellowish red(pad-dry heat).

Example XXXXVII 2.04 parts of 2cyano-4-nitro-aniline are diazotized inthe manner described in example XXXlV but with an addition of parts byvolume of acetic acid. The filtered solution is coupled with 4.63 partsof meta-bis-(N-methane-sulfonyl)- amino-N,N-di(2cyanoethyl)-aniline inacetic acid (150 parts) in the manner described in example XXXlV. Thedyestufi' obtained which corresponds to the formula CHzCHzCN l ONN(SO2CH3)2 dyes polyester fiber red violet (high temperature) and dullbluish red (pad-dry heat).

Example XXXXVlll To a suspension of m-nitroaniline in dry benzene, wasadded a little more than the calculated amount of methane sulfonylchloride and an acid binding agent, triethylamine. The mixture wasboiled at reflux for 15 hours and worked up in the usual way to givemeta-bis-(Nmeth:ane-sulfonyl)-amino-mnitroaniline, m.p. 168 C.

N( S OQCHa):

it was reduced with R/Ni as catalyst at 50 C. to givemetabis-(N'-methane-sulfonyl)-amino-phenylene diamine, whichcrystallized from alcohol, m.p. 200-20 1 C.

described in example XXXlV. The dyestuff obtained which corresponds tothe formula CHzCHr UK CHECH? OH dyes polyester fiber bluish pink (hightemperature) and reddish blue (pad-dry heat).

Example IL 1.63 Parts of 2-cyano-4-nitroaniline are diazotized in themanner described in example XXXIV but with an addition of 5 parts ofacetic acid. The filtered solution is coupled with 3.52 parts ofmeta-bis-(N"methane-sulfonyl)-amino-N,N-di- (2-hydroxyethyl)-aniline inwater (300 parts) and alcohol (50 parts) in the manner described inexample XXXlV. The dyestuff obtained which corresponds to the formuladyes polyester fiber violet (high temperature) and reddish violetpad-dry heat).

Example L 2.04 Parts of 2:6-dichloro-4-nitroaniline are diazotized inthe manner described in example XXXlV. The filtered solution is coupledwith 3.52 parts ofmeta.-bi-(N'-methane-sulfonyl)-amino-N,N-di-(2-hydroxy-ethyl)-aniline inwater (300 parts) and alcohol (50 parts) in the manner described inexample XXXIV. The dyestuff obtained which corresponds to the formuladyes polyester fiber dull bluish red (high temperature) and reddishbrown (pad-dry heat).

Example LlMeta-bis-(N-methane-sulfonyl)-amino-N,N-di-(2-hydroxyethyl)-aniline wasrefluxed with acetic anhydride to givemeta-bis-(N-methane-sulfonyl-amino-N,N-di(Z-acetoxyethyl)-aniline whichcrystallized from dilute alcohol, m.p. l08-l09 C.

OH2CH2OCOOH3 cmomocoom N(SO2CHa)1 1.73 Parts of 2-chloro-4-nitroanilineare diazotized in the manner described in example XXXIV. The filteredsolution is coupled with 4.36 parts of meta-bis-(N'-methane-sulfonyl)-amino-N,N-di-(Z-acetoxy-ethyl)-aniline in acetic acid (200 parts) in themanner described in example XXXIV. The dyestuff obtained whichcorresponds to the formula CHzCHz O C OCH:

dyes polyester fiber red (high temperature) and yellowish red (pad-dryheat).

Example LII 1.63 Parts of 2-cya.no-4-nitroaniline are diazotized in themanner described in example XXXIV but with an addition of 5 parts ofacetic acid. The filtered solution is coupled with 4.36 parts ofmeta-bis-(N'-methane-sulfonyl-amino-N,N-di(2- acetoxy-ethyl)-aniline inacetic acid (200 parts) in the manner described in example XXXIV. Thedyestuff obtained which corresponds to the formula ON N(SO2CH3)2CHzCI-DOC CH3 N CHzCHzO C OCH:

violet (high temperature) and dyes polyester fiber reddish bluish red(pad-dry heat).

Example Llll 2.04 parts of 2:6-dichloro-4-nitroaniline are diazotized inthe manner described in example XXXIV. The filtered solution is coupledwith 4.36 parts of meta-bis-(N-methane-sulfonyl)-amino-N,N-di-(2-acetoxy-ethyl)-aniline in acetic acid (200 parts) in the mannerdescribed in example XXXIV. The dyestuff obtained which corresponds tothe formula l CH2OH1OGOCH3 NOz- N=N N\ C1 N(SOzCHa) 2 whereinD-represents a diazo residue of the benzene series, R is lower alkyl, Ris lower alkyl or phenyl which may be substituted by bromine or methyl,each of R and R is alkyl containing up to four carbon atoms, alkylcarbonyloxyalkyl containing up to five carbon atoms, hydroxyethyl, orcyanoethyl.

3. A monoazo dyestuff according to claim 2 which corresponds to theformula 4. A monoazo dyestuff according to claim 2 which corresponds tothe formula 5. A monoazo dyestuff according to claim 2 which correspondsto the formula 6. A monoazo dyestuff according to claim 2 whichcorresponds to the formula CH2CHz-O CO CH UNITED STATES PA OFFICE GETmcAT m Ved Parkash Kubba Inventmfls) It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 20, line 6, delete "30'" and substitute 2 the middle portion ofthe formula. of claim 3 should read Signed and sealed this 37th day ofJune 1 972 (SEAL) Attest:

EDWARD MmFLETGHEmJR... ROBERT GOTTSGHALK Attesting Officer Commissionerof Patents

2. A monoazo dyestuff of the formula
 3. A monoazo dyestuff according toclaim 2 which corresponds to the formula
 4. A monoazo dyestuff accordingto claim 2 which corresponds to the formula
 5. A monoazo dyestuffaccording to claim 2 which corresponds to the formula
 6. A monoazodyestuff according to claim 2 which corresponds to the formula